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Publication numberUS3395036 A
Publication typeGrant
Publication dateJul 30, 1968
Filing dateMay 17, 1965
Priority dateMay 17, 1965
Also published asDE1594991A1, DE1594991B2, DE1594991C3
Publication numberUS 3395036 A, US 3395036A, US-A-3395036, US3395036 A, US3395036A
InventorsCampbell James Kermit
Original AssigneeDow Corning
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Process for post-finishing pigmented glass fabric
US 3395036 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

Unite 3,395,036 PROCESS FOR PQST-FINESHING PI-GMENTED GLASS FABRIC James Kermit Campbell, Midland, Mich., assignor to Dow Corning Corporation, Midland, Mich., a corporation of Michigan No Drawing. Filed May 17, 1965, Ser. No. 456,544 2 Claims. (Cl. 117-126) ABSTRACT OF THE DISCLOSURE This application relates to a method for permanent fixing of pigments on glass fabric through the application of a treating solution, following the pigmentiug of the glass fabric.

It is Well known that piments do not adhere to glass fabric in a satisfactory manner, even when an organic binder is used. They are easily removed by washing the fabric.

The post-finishing composition of this invention is highly effective in producing the permanent adhesion of pigments to glass fabric, rendering the colored fabric washable. Further advantages of the composition of this invention are that it renders the fabric on which it is placed hydrophobic, and that it improves both the Wet and dry abrasion resistance of the pigment on the fabric. The color of the fabric is generally not altered by the above treatment.

This application relates to a post finish for pigmented glass fabric consisting essentially of (a) from 1 to 8 parts by weight of RSiX where R is selected from the group consisting of monovalent aliphatic hydrocarbon radicals of no more than 3 carbon atoms, monovalent aryl and alkaryl radicals, and beta-perfiuoroalkylethyl radicals; and X is selected from the group consisting of alcoholate radicals, lower acyloxy radicals, lower dihydrocarbyl-substituted isocyanoxy radicals, and the isocyanate radicals, (b) from 0.5 to 4 parts by Weight of a compound selected from the group consisting of (l) MX where M is selected from the group consisting of titanium and zirconium and X is defined above, and (2) a reaction product of (1) with a beta-diketoester or a beta-diketone, the ratio of the weights of (a) to (b) being from 1:1 to :1, and (c) 100 parts by Weight of water, the pH of said post finish being from 2.5 to 6.0.

R can be any monovalent hydrocarbon radical as described above such as methyl, ethyl, isopropyl, ethynyl, or vinyl. R can also be any monovalent aryl or alkaryl radical, such as phenyl, xenyl, naphthyl, or tolyl. Finally, R can be any beta-perfluoroalkylethyl radical such as 3,3,3-trifluoropropyl, C F CH CH C F CH CH 01' C12F25CH2CH2-.

By alcoholate radical is meant any organic radical having a free valence of the form ECO, the radical being derived from an alcohol, which in the broad sense is any organic compound with a ECOH bond.

X can be alcoholate radical, e.g. any alkoxy or alkoxyalkoxy radical such as methoxy, ethoxy, isobutoxy, 2- ethylhexoxy, beta-methoxyethoxy, or beta-ethoxyethoxy; alkyleneoxy radicals such as ethylene glycolate or glycer- States Patent 0 ate, and substituted alcoholates such as NH CH CH O or (NH CCH O; any lower acyloxy radical such as formate, acetate, lactate or butyrate; and any isocyanoxy radical as described above such as (b) can be the reaction product of MX with beta diketones or beta diketoesters which have the formula 0 0 Q CHQK DQ where Q is any monovalent aliphatic hydrocarbon radical, Q is hydrogen or any monovalent aliphatic hydrocarbon radical, and Q is a monovalent aliphatic hydrocarbon radical or an aliphatic hydrocarbonoxy radical. Examples of such reaction products where M is zirconium are listed in US. Patent 2,884,393, and a method of preparation of these reaction products i shown.

The corresponding titanium reaction products are analogous to the zirconium compounds of the above patent. Examples of both of these reaction products are CH2=CHCH tetra (methoxyethyl) titanate, bis (acetylacetonyl) diisopropyl titanate,

0 CH CH C H1OTiOOH- CHZN O CHzCHz [H0 0 o CH(CH 01421, [HO 0 0 (oHp ohTnom (CH COOCH O) Ti, diisopropyldiacetoxy titanate, and

Ingredients (a) and (b) can be polymeric as in the case where X is the alcoholate residue of glycerine or ethylene glycol.

Small amounts of additional ingredients may be mixed with the above formulation without departing from the spirit of this invention. Acids such as acetic, formic, or phosphoric acid can be added to raise the pH to a more desirable range, or ammonia can be added to lower the pH. Dyes or pigments can be directly placed in the treating composition to dye the fabric and fix the dye in one step. Also, the presence of a small amount of zinc acetate in the mixture tends to render the glass fabric more water-repellent.

The composition of this invention is applied to pigmented glass fabric simply by dipping the fabric in a bath of the composition, and drying the dipped fabric at about 300 to 500 F. for about 1 to 5 minutes. The preferred temperature range is from 350 to 450 F.

Alternatively, the composition of this invention can be sprayed on the fabric or applied in any other suitable manner, the drying process being as shown above.

It is not absolutely required that the treated glass fabric be heat-cured. The composition of this invention will cure on the fabric in a matter of hours at room temperature.

The nature of the pigment on the glass is not critical; many methods of coloring glass fabric are well known, and many different binders can be used. An acrylic latex is highly suitable as a binder for the pigment, as are acrylonitrile butadiene-styrene, polyvinylbutyral, and other organic resins.

As a preferred embodiment, this application relates to a post finish for pigmented glass fabric consisting essentially of (a) from 1 to 3 parts by weight of R'Si(OR") where R is selected from the group consisting of methyl, phenyl, and vinyl, and R" is selected from the group consisting of methyl and ethyl, (b) from 0.4 to 1.5 parts by weight of zirconium acetate, (c) 100 parts by weight of water, and (d) from 0.1 to 0.3 part by weight of zinc acetate, there being sufiicient acetic acid present to impart to the mixture a pH of 3.0 to 6.0, and there being no more of (b) present than (a).

It is preferred for R to be methyl. Compositions where R is methyl yield the greatest wash-durability.

Compositions where R is phenyl or propyl impart a softer hand to the glass fabric than when R is methyl. If a very stiff hand is desired, R should be vinyl, in whole or in part.

Ingredients (a) and (b) can each consist of mixtures: e.g. ingredient (a) can be an equimolar mixture of methyltriacetoxysilane and 3,3,3 trifluoropropyltriethoxysilane.

The following examples are illustrative only and should not be construed as limiting the invention, which is properly delineated in the appended claims.

Example 1 (a) To 100 parts by weight of water there was added 2 parts of methyltrimethoxysilane, 0.83 part of zirconium tetraacetate, 0.16 part of zinc acetate, and 0.21 part of acetic acid.

Glass fabric which had been pigmented with an inorganic pigment and an ethyl acrylate binder was dipped in this mixture and pressed at 15 p.s.i. to remove excess solution. The fabric was then air dried and cured for 1 /2 minutes at 380 F.

The cured fabric was found to be moderately waterrepellent. The fabric was machine-washed with Tide detergent three times with only a trace of fading of the pigment coating.

The cured fabric exhibited excellent abrasion resistance, in that the pigment coating was not easily removed by rubbing.

(b) Untreated, pigmented glass fabric exhibited low water-repellency, and the pigment was easily removable by either washing or rubbing.

Example 2 (a) To 100 parts by weight of water there was added 1 part of methyltrimethoxysilane, 0.83 part of zirconium tetraacetate, 0.16 part of zinc acetate, and 0.21 part of acetic acid.

(b) To 100 parts by weight of water there was added 2 parts of methyltrirnethoxysilane, 0.41 part of zirconium tetraacetate, 0.08 part of zinc acetate, and 0.20 part of acetic acid.

(c) To parts by weight of water there was added 1 part of methyltrimethoxysilane, 0.41 part of zirconium tetraacetate, 0.08 part of zinc acetate, and 0.20 part of acetic acid.

Samples of pigmented glass fabric were dipped into these mixtures and cured in the manner of Example 1(a), yielding treated glass fabric having properties similar to the fabric of Example 1(a).

Example 3 (a) To 100 parts by weight of water there was added 1.5 parts of methyltrimethoxysilane, 0.5 part of n-propyltrimethoxysilane, 0.83 part of zirconium tetraacetate, 0.16 part of zinc acetate, and 0.21 part of acetic acid.

(b) To 100 parts by weight of water there was added 1.5 parts of methyltrimethoxysilane, 0.5 part of phenyltrimethoxysilane, 0.83 part of zirconium tetraacetate, 0.16 part of zinc acetate, and 0.21 part of acetic acid.

Samples of pigmented glass fabric were dipped into these mixtures and cured in the manner of Example 1(a), yielding treated glass fabric having properties similar to the fabric of Example 1(a).

The fabric treated with the mixture of 3(a) had a softer hand than the fabric of Example 1(a).

Example 4 When 100 parts by weight of water are added to 4 parts of 02115 OHFCHSI ONC\ 1 part of tetraethyltitanate, and sufiicient CO to impart a pH of 5.0 to the mixture, a glass fabric finishing composition is formed.

Glass fabric which had been pigmented with an inorganic pigment and an acrylonitrile-butadiene-styrene binder was dipped in this mixture, dried, and cured at 400 F. for 3 minutes.

The pigmented glass fabric was washable without fading, and the pigment exhibited good abrasion resistance.

Example 5 Equivalent results are obtained when 100 parts by weight of water are mixed with 6 parts of 3,3,3-trifluoropropyltrimethoxysilane, 3 parts of Zr(OCH CH OCH and 0.01 part of HCl, and the resulting composition is used as in Example 4.

Example 6 Equivalent results are obtained when 100 parts by weight of water are mixed with 3 parts of CH OSMNCO);

and 3 parts of titanium tetraacetate, and the resulting composition is used as in Example 4.

Example 7 Equivalent results are obtained when 100 parts by weight of water are mixed with 1 part of and 1 part of CH C=O o t 111 ZrO OH; CH3CO 3 and the resulting composition is used in Example 4.

That which is claimed is:

1. A process for post-finishing glass fabrics comprising applying to pigmented glass fabric a composition consisting essentially of (a) from 1 to 8 parts by weight of RSiX where R is selected from the group consisting of monovalent 5 aliphatic hydrocarbon radicals of no more than 3 carbon atoms and phenyl, and X is an alkoxy radical, (b) from 0.5 to 4 parts by weight of zirconium acetate,

and (c) 100 parts by weight of water, the pH of said postfinish mixture being from 2.5 to 6.0, and thereafter allowing said composition to cure. 2. The process of claim 1 where from 0.1 to 0.3 part by weight zinc acetate is present.

References Cited UNITED STATES PATENTS 3,244,541 4/1966 Fain 1062 6 Vescia et a1. 117----161 Lawsberg 8-8 Roff 8-8 Beutler 260-4293 Mazocchi 117124 Ferrigno 106-287 Vincent 117126 Campbell 117126 Vincent 117126 JAMES A. SEIDLECK, Primary Examiner.

T. MORRIS, Assistant Examiner.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2919172 *Nov 20, 1952Dec 29, 1959Gen Aniline & Film CorpMethod of coloring woven glass fibers
US2919173 *May 20, 1958Dec 29, 1959Stevens & Co Inc J PDyed fibrous glass material and process of dyeing
US2927870 *Aug 28, 1956Mar 8, 1960Dow CorningZirconium acetate-zinc acetate catalyzed organohydrogenosiloxane emulsions and the treatment of fabrics therewith
US2938812 *Apr 21, 1954May 31, 1960Owens Corning Fiberglass CorpTreated glass fibers and compositions for use in same
US3231404 *Apr 26, 1963Jan 25, 1966Minerals & Chem Philipp CorpMarking composition
US3244541 *Feb 3, 1961Apr 5, 196629 West Fifteenth Street CorpWater-repellent compositions and methods of making same
US3258382 *Apr 19, 1961Jun 28, 1966Dow CorningIn situ hydrolysis of alkoxy silanes containing orthotitanate catalysts
US3262810 *Jul 20, 1962Jul 26, 1966Dow CorningGlass cloth
US3262830 *Apr 19, 1961Jul 26, 1966Dow CorningOrganosilicon molding compositions containing orthotitanate catalysts
US3313649 *Dec 9, 1964Apr 11, 1967Basf AgDyed and printed glass fibers and a process for dyeing and printing glass fibers
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3687882 *Apr 29, 1971Aug 29, 1972Nexcel CorpSilane-titanate dispersions for coating aluminum
US4311738 *May 27, 1980Jan 19, 1982Dow Corning CorporationMethod for rendering non-ferrous metals corrosion resistant
US4746366 *Mar 17, 1986May 24, 1988Fraunhofer-Gesellschaft Zur Forderung Der Angewandten Forschung E.V.Process and lacquer for the production of scratch-resistant coatings
US5008153 *Dec 8, 1988Apr 16, 1991Ppg Industries, Inc.Corrosion inhibitive pretreatment for "copper-free" mirrors
US5192364 *Jun 25, 1991Mar 9, 1993Shin-Etsu Chemical Co., Ltd.Primer compositions
US5294252 *Jul 27, 1992Mar 15, 1994Gun Julio OComposition for producing a monomolecular film, on surfaces of various materials
US5318618 *Nov 19, 1992Jun 7, 1994Shin-Etsu Chemical Co., Ltd.Primer compositions
US5357024 *Jul 19, 1993Oct 18, 1994Essilor InternationalMethod for preparing a polysiloxane and titanate composition for high refractive index coatings
Classifications
U.S. Classification428/428, 106/287.13, 106/287.14, 106/287.19, 106/287.16, 106/287.17
International ClassificationD06M15/37, D06M15/643, C08G77/00, C08G77/08, C03C25/10, D06P1/44
Cooperative ClassificationD06P1/44, D06M15/6436, C03C25/1095, C08G77/08
European ClassificationD06M15/643D, D06P1/44, C08G77/08, C03C25/10Q